Producing transparent colors in lacquers



UNITED STATES PATENT OFFICE PRODUCING TRANSPARENT COLORS IN LACQUERS Heinrich Kobbe, Mannheim, Germany, assignor to General Aniline & Film Corporation, a corporation of Delaware No Drawing. Application May 27, 1937, Serial N0.145,053. In Germany June 11, 1936 8 Claims. (Cl. 134-26) The present invention relates to productionof each other. Instead of ethylene glycol derivatransparent colors in lacquers. tives, there may also be used derivatives of glycols For the coloring of lacquers which have been of higher molecular weight, such as those of prepared with the aid of chemical drying binding propylene or butylene glycol or the polyglycols.

agents, such as linseed oil, wood oil or condensa- The solvent or solvent mixture best suited for the tion products of polyhydric alcohols, polybasic dyestuff or lake used may be readily ascertained carboxylic acids and drying oils, if desired with by asimple preliminary experiment. an addition of natural or synthetic resins, there Dyestuffs soluble in oxygen-containing organic have hitherto been used organic dyestufis soluble solvents which are suitable for coloring drying 0 in hydrocarbons, as for example, simple azo dyelacquers are in particular those dyestuffs which 10 stufi's and anthraquinone compounds. Such have already been used for dyeing cellulose ester dyestulfs are, however, usually not sufficiently and ether lacquers as well as spirit resin lacquers. fast to light and are as a rule not so stable to heat There may be mentioned for example the salts of that the lacquers colored therewith can be dried water-insoluble acid dyestuffs containing saltat elevated temperatures. It has also already o n g p W Organic bases, Such as are 15 been proposed to color lacquers of the said kind described for example in the U. S. Patents Nos. by incorporating therewith transparent pigments 1,800,299, 1,800,300 and 1,860,036, and also the or color lakes insoluble in organic solvents. This omplex met l compo nds f an d u process is very diflicult to carry out in practice n pa c aZO dyestllfis, Which are Soluble in and frequently does not yield transparent colora- Oxyg -Co a g SOIVentS- The Salts prepared 20 tions free from objection. y from organic dyestulT bases and complex heavy I have now found that lacquers which have metal compounds of organic dyestufis cont ini been prepared with the use of. chemical dryin sulphonic and carboxylic groups may also be used. binding agents can be colored transparently in The salts p p from phthalocyanine an excellent manner by incorporating therewith phon c a ids nd o i b e r also especially solutions of organic dyestuffs which are soluble suitable. V r s z as f r example in organic solvents containing oxygen in solvents phenyl-1.3naphthy1e e a D acid of the said kind. The term organic dyestuffs para aminodiphe y o Ortho Su ph c also includes the salts of acid dyestuffs with oracid Which are o le n th said s lven m y ga c bases S lCh as cyclohexylamine. The also be .employed. In this connection see Schultz 30 amounts of oxygen-containing solvents necessary Farbstofitabellen, VII VOL N0. 974, and the for the dissolution of the dyestuffs are relatively C0101 IndeX, 1924, small so that by using the process there are ob- Th col r d ry g l q p pa according tained Without difficulty well-colored transparent to h s invention Y d Valuable transparent C lacquers of excellent fastness to light which may in s w h n a y sp n ha d t ve y 5 also be directly annealed at elevated temoo ast ss o light By reason of their good peratures. stability to heat, the lacquers may also be an- The process according to this invention may be hea ed Without t e good properties of the Colors used both with oil lacquers, as for example those being p d therebyof linseed oil-stand oil, wood oil and a natural he fo l w n x p W l f r h r ill r 0 or synthetic resin and with pure stand oil la how the said invention may be carried out in quers,0r with lacquers derived from condensation practice but the invention is not restricted to products of polyhydric alcohols with polybasic these examples- The parts are y Weightcarboxylic acids and drying oils. Oxidation ac- Example. 1

celerators, as for example metal salts of naphthenic acids, of linoleic acid or of abietic acid may be added to the lacquers if desired pound of the dyestulf: l-nitro-Z-aminophenyl-fi- As solvents for the dyestulis there may be men- Sulphonic acid"1'pheny]'3'methyl's'pyrazolone t d for example alcohols, in particular m0n0 are dissolved in 100 parts of benzyl alcohol and hydric 1 h 1 as for example butanol or benzyl the solution is added to 1000 parts of a mixture 50 alcohol, and also the esters of such alcohols with of 600 parts of linseed Oil-Stand Oil and 400 parts aliphatic monocarboxylic acids, others, as for of lacquer benzine. The lacquer thus p p example ethylene glycol monoand di-ether yields orange colored transparent coatings on glycol ether esters and glycol monoand ,dimetals, w y the drying y b Car ed out esters, as well as mixtures of these solvents with attemperatures up to about C. or if desired 55 From 5 to 10 parts of the chromium comsomewhat higher. If desired 6 parts of a lead cobalt-manganese naphthenate (cobalt content 1.5 per cent, manganese content 1.5 per cent, lead eontent24 per cent) may be added to the colored lacquer. A lacquer treated in this way dries in the ordinary way at ordinary temperature.

Instead of the said dyestufi there may be used the same amount of the complex chromium compounds of the azo dyestuff: 4-nitro-2-aminophenol-G-sulphonic acid acetoacetic acid anilide or the azo dyestuff: 4-chlor-2-aminophenol- 6-sulphonic acid- 1-phenyl-3-methyl-5-pyrazolone. In the former case a brilliant yellow, and in the latter case a reddish orange coating of good properties as regards fastness is obtained.

Example 2 From to parts of the salt prepared from dicyclo-hexylamine and the azo dyestuff: 1- aminobenzene-Z-sulphonic acid l-(2-sulphophenyl) -5-pyrazolone-3-carboxylic acid are dissolved in 100 parts of gylcol monoacetate and the solution is added to 1000 parts of a lacquer consisting of, 400 parts of a condensation product of 3 molecular proportions of phthalic anhydride with 3 molecular proportions of glycerine and 1 molecular proportion of linseed oil and 600 parts of a mixture of lacquer benzine and oil of turpentine in the ratio of 3:1. The colored lacquer thus obtained may be annealed at temperatures up to 130 C., or if desired still higher, and no discoloration results. It has a very good fastness to light and excellent transparency.

Instead of the above mentioned condensation product, condensation products of. other compositions derived from polybasic acids, polyhydric alcohols and monobasic carboxylic acids may be used, and the dyestuif may be the said chromazo dyestuif or may be replaced by a small amount of dyestuffs of the following composition:

Example 3 From 5 to 10 parts of a salt prepared from Rhodamine B (Schultz, Farbstofftabellen, 7th edition, No. 864) and the complex chromium compound of the monoazo dyestuff: 4-nitro-2- aminophenol-G-sulphonic acidacetoacetic acid anilide are dissolved in 100 parts of glycol monoacetate or benzyl alcohol and the resulting solu tion is added to 1000 parts of one of the lacquers described in Example 2. With the resulting colored lacquer there are obtained transparent red coatings very fast to light which also retain their good transparency after annealing.

By using a salt prepared from Rhodamine B and the complex chromium compound of the azo dyestufr": 6-nitro2-aminophencl-4-sulphonic acid- 1-phenyl-3-methyl-5-pyrazolone instead of the above mentioned salt, blue-red coatings of equally good properties are obtained.

What I claim is:

l. A process of producing transparently colored lacquers which contain as film-forming material a chemically drying binding agent selected from the class consisting of drying oils and condensation products of. polyhydric alcohols, polybasic carboxylic acids and drying oils which comprises incorporating therewith solutions of dyestuffs selected from the group consisting of complex metal compounds of azodyestufis and organic dyestuffs containing sulfonic acid groups which are neutralized by a nitrogencontaining organic base in organic solvents containing oxygen and selected from the class consisting of butanol, benzyl alcohol, the esters thereof with aliphatic monocarboxylic acids, glycol ethers, glycol ether esters and glycol esters, which dyestuffs are insoluble in the lacquers to be dyed.

2. A process of producing transparently colored lacquers which contain as film-forming material a chemically drying binding agent selected from the class consisting of drying oils and condensation products of. polyhydric alcohols, polybasic carboxylic acids and drying oils which comprises incorporating therewith solutions of dyestuffs selected from the group consisting of complex metal compounds of azodyestuffs and organic dyestuffs containing sulfonic acid groups which are neutralized by a nitrogencontaining organic base in a glycol ester, which dyestuffs are insoluble in the lacquers to be dyed.

3. A process of producing transparently colored lacquers which contain as film-forming material a chemically drying binding agent selected from the class consisting of drying oils and condensation products of, polyhydric alcohols, polybasic carboxylic acids and drying oils which comprises incorporating therewith solu- I tions of dyestuffs selected from the group consisting of complex metal compounds of azodyestuffs and organic dyestuffs containing sulfonic acid groups which are neutralized by a nitrogencontaining organic base in butanol, which dyestuffs are insoluble in the lacquers to be dyed.

4. A process of. producing transparently colored lacquers which contain as film-forming material a chemically drying binding agent selected from the class consisting of drying oils and condensation products of polyhydric alcohols, polybasic carboxylic acids and drying oils which comprises incorporating therewith solutions of dyestufis selected from the group consisting of complex metal compounds of azodyestuffs and organic dyestuffs containing sulfonic acid groups which are neutralized by a nitrogencontaining organic base in benzyl alcohol, which dyestuffs are insoluble in the lacquers to be dyed.

5. A composition of matter comprising a lacquer which contains as film-forming material a chemically drying binding agent selected from the class consisting of drying oils and condensation products of polyhydric alcohols, polybasic carboxylic acids and drying oils and a dyestufi selected from the group consisting of complex metal compounds of azodyestuffs and organic dyestuffs containing sulfonic acid groups which are neutralized by a nitrogen-containing organic base which dyestuff is soluble in organic solvents containing oxygen and selected from the class consisting of. butanol, benzyl alcohol, the esters thereof with aliphatic monocarboxylic acids, glycol ethers, glycol ether esters and glycol esters but insoluble in the lacquer of the composition.

6. A composition of matter comprising a lacquer which contains as film-forming material a chemically drying binding agent selected from the class consisting of drying oils and condensation products of polyhydric alcohols, polybasic carboxylic acids and drying oils and a dyestuff selected from the group consisting of complex metal compounds of azodyestuffs and organic dyestuffs containing sulfonic acid groups which are neutralized by a nitrogen-containing organic base which dyestufi is soluble in a glycol ester but insoluble in the lacquer of the composition.

7. A composition of matter comprising a lacquer which contains as film-forming material a chemically drying binding agent selected from the class consisting of drying oils and condensation products of polyhydric alcohols, polybasic carboxylic acids and drying oils and a dyestufi selected from the group consisting of complex metal compounds of azodyestuffs and organic dyestuffs containing sulfonic acid groups which selected from the group consisting of complex 10 metal compounds of azodyestufis and organic dyestuffs containing sulfonic acid groups which are neutralized by a nitrogen-containing organic base which dyestuff is soluble in benzyl alcohol but insoluble in the lacquer of the composition. 15

HEINRICH KOCBBE. 

